A novel kind of PVDF-HFP(polyvinylidene fluoride-hexafluoropro-pylene)-based polymer electrolyte composite membrane for lithium-ion battery was prepared. Inorganic TiO2 nanopowders in composite were dealt with solid super-acidization. Series of characterizations were carried on, such as surface acid strength H0, XRD analysis, electrolyte absorbency, and electrochemical impedance spectroscopy. PE non-woven fabrics were introduced as the reinforced materials, which were soaked to prepare the composite membranes, and then assembled to get the resulted lithium-ion battery. Performance tests indicated that the lithium-ion battery had good electrochemical performance.